Process for dyeing furs, hairs, and feathers



Patented Declf26, 1933 PATENT OFF-ICE PROCESS FOR- :DYEING FURS, HAIRS, AND vFEATHERS Erich 'Lehmann, Bitterfeld, and Hans Wassenegger; Dessau in 1 rAnhalt, Germany, as-

1 signors to General Aniline Works, Inc., New York, N. a corporation of Delaware No Drawing. Application June 9, 1933, Serial No.675,144,-' and in Germany May 6, 1932 9 Claims.

Application has been filed in Germany, May

Our invention relates to a new process for dyeing furs, hairs and feathers.

We have found that for dyeing furs, hairs and feathers in the presence of an oxidizing agent,

in which R means phenyl or a substituted phenyl, such as halogenophenyl,.alkylphenyl, hydroxy phenyl, alkoxyphenyl, X means alkyl or hydroxyalkyl, z and a stand for hydrogen, alkyl or hydroxyalkyl and n for l or 2.

These substituted diamines of the benzene series may be used either alone-especially in the case of paradiamines-or together with other well known dyes for pelts and new shades are obtainable in this manner which could be obtained until yet, if at all, only by complicated dyeing processes.

The manufacture'of the sulfides in question may be carried out, for instance, according to well known processes by treating diamines or the corresponding nitro compounds containing a radicle capable of exchange with mercaptans followed, if necessary, by reduction of the nitro group or groups.

Thus, for instance, 2.4-dinitrochlorobenzcne may be treated with ethylmercaptan. By treating the reaction product'with a reducing agent 2.4- diaminophenylethylsulfide (1) is obtainable which, together with paraphenylenediamine, dyes furs bright black shades of greenish tinge which are not obtainable with other dyes,

The following examples serve to illustrate our invention, the parts being by weight:-

Example 1.-3 parts of a mixture of 80 parts of paraphenylenediamine and 20 parts of 2.4-diaminophenylethylsulfide (l) are dissolved in the form of their salts with hydrochloric acid in 1000 parts of water. Ammonia is added for binding w the hydrochloric acid and 30 parts of hydrogen Example 2.--White rabbit skinmordanted with a chromium or copper salt is treated with an aqueous solution, 1000 parts of which contain 3 parts of a mixture consisting of 80 parts of paraphenylenediamine and parts of 2.4-diaminobenzenehydroxyethylsulfide (l) of the formula and parts of a 3% hydrogen superoxide solution. After 3 hours the skin is dyed a clear, somewhat greenish black.

Example 3.The skin is treated with an aqueous solution, 1000 parts of which contain 2 parts of 2.5-diamino-l-methoxyphenylethylsulfide (4) and 20 parts of a 3% hydrogen superoxide solution. A skin mordanted with chromium salts is dyed a dull bluish red brown; skin mordanted with copper salts a greyish brown, skin mordanted with iron salts a dark grey.

2.5 diamino 1 chlorophenylethylsulfide (4) yields similar tints having a somewhat yellowish tinge.

Example 4.-White rabbit skin mordanted with a copper salt is treated with an aqueous solution 1000 parts of which contain 3 parts of 5- amino-2-dihydroxypropylamino-l-chlorophenylethylsulfide (4) of the formula and 30 parts of a 3% hydrogen superoxide solution. The skin is dyed a clear yellowish brown.

Diamines containing twice the thioether radicle are likewise suitable for dyeing furs, hairs and feathers and we enumerate, for instance,

1.3-diaminophenyldi(ethylsulflde) (4.6) and 1.3- diaminophem'ldflhydroxyethylsulflde) (4.6) of the formula HO-CHa-GH which are obtainable by treating dinitrodichlorobenzene with ethylmercaptan or hydroxyethylmercaptan and by reducing the nitro groups.

It is obvious that our invention is not limited to the foregoing examples or to the specific details given therein. Thus, the dyeing of the furs may be carried out in a neutral, an acid or an alkaline dyeing bath. The thioethers of the diamines in question may contain in the benzene nucleus other substituents than those indicated in the examples. As such substituents we enumerate the hydroxy group and the alkyl group. One of the amino groups may be substituted by alkyl or hydroxyalkyl radicles to form a secondary or tertiary amine. On the other hand, instead of ethyl or hydroxyethyl there may be bound with the sulfur another alkyl or monoor polyhydroxyalkyl radicle.

As may be seen from Examples 1 and 2, we

prefer to us the thioethers of metadiamines together with other dyes for furs and we have exemplified this possibility by mentioning paraphenylenediamine. As other dyes which may be used in combination with the thioethers in question, we enumerate chloroor nitroparaphenylenediamine, 4-amino-1-dimethylaminobenzene, 4-amino-1-hydroxybenzene, 2-nitro-4-amino-1- hydroxybenzene, 4-chlor'o-2-amino-l-hydroxybenzene, 4.4'-diaminodiphenylamine, 4-dimethylaminodiphenylamine and similar compounds well known in the art.

What we claim is:

1. The process for dyeing furs, hairs or feathers which comprises treating the said material in a dyeing bath containing hydrogen superoxide and a diamine of thegeneral formula HIN in which It means phenyl, halogenophenyl, hydroxyphenyl, alkoxyphenyl or alkylphenyl, and X means alkyl or hydroxyalkyl, z and z stand for hydrogen, alkyl or hydroxyalkyl and n for 1 or 2.

2. The process for dyeing furs, hairs or feathers which comprises treating the said material in a dyeing bath containing hydrogen superoxide and a diamine of the general formula in which R means phenyl, halogenophenyl, hydroxyphenyl, alkoxyphenyl or alkylphenyl, and X means alkyl or hydroxyalkyl, z and a stand for hydrogen, alkyl or hydroxyalkyl and n for 1 or 2, and a further dye for pelts of the group consisting of paradiamines and parahydroxyamino compounds of the benzene series.

3. The process for dyeing furs, hairs or feathers which comprises treating the said material in a dyeing bath containing hydrogen superoxide and a diamine of the general formula in which R means phenyl, halogenophenyl, hydroxyphenyl, alkoxyphenyl or alkylphenyl and X means alkyl or hydroxyalkyl.

4. The process for dyeing furs, hairs or feathers which comprises treating the said material in a. dyeing bath containing hydrogen superoxide and a diamine of the general formula N Hz alkyl-S- f in which 3 means hydrogen, halogen, alkoxy, alkyl or alkoxy and a further dye for pelts of the-1 group consisting of paradiamines and parahydroxyamino compounds of the benzene series.

6. The process for dyeing furs, hairs or feathers which comprises treating the said material in a dyeing bath containing hydrogen superoxide and a diamine of the general formula elkyllac in which 1/ means hydrogen, halogen, alkoxy, alkyl or alkoxy and paraphenylenediamine. 13!

7. The process for dyeing furs, hairs or feathers which comprises treating the said material in a dyeing bath containing hydrogen superoxide and the diamine of the formula 0 HtCrand paraphenylenediamine.

8. The process for dyeing furs, hairs or feathers which comprises treating the said material 150 in a dyeing bath containing hydrogen superoxide and the diamine 01. the formula are which comprises treating the said material in a dyeing bath containing hydrogen superoxide and the diamine of the formula ERICH LEI-MANN. HANS WASS ENEGGER. 

